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Iridium‐Catalyzed Enantioselective Allylic Substitution of Unstabilized Enolates Derived from α,β‐Unsaturated Ketones
Author(s) -
Chen Ming,
Hartwig John F.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201403844
Subject(s) - allylic rearrangement , enantioselective synthesis , silylation , chemistry , iridium , catalysis , substitution reaction , selectivity , substitution (logic) , yield (engineering) , combinatorial chemistry , organic chemistry , materials science , computer science , metallurgy , programming language
We report Ir‐catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from α,β‐unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62–94 % yield with 90–98 % ee and >20:1 branched‐to‐linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI‐9826.